SURFACE CHEMISTRY
SURFACE CHEMISTRY
SYNOPSIS
GENERAL CHARACTERISTICS
Surface chemistry which deals with the
henomena that occur at the surfaces or
terfaces, i.e., at the boundary separating the
two bulk phases.
Surface areameans the top most layer upto the
100nm depth.
T h e interface is represented bya hyphen orslash
between bulk phases
ELEMENTARY CONCEPT OF
ABSORPTIOPN,ADSORPTION
SORPTION & DESORPTION
Adsorption: The accumulation of molecular
species at the surfàce rather than in the bulk ofa
solid or liquid.
The molecular species or substances, which
concentrates or accumulates at the surface is
termed as adsorbate.
Adsorbate can be gas, liquid or solid.
> The material or substance on the surface ofwhich
the adsorption takes place is called adsorbent.
Adsorbent can be solid or liquid but not gas
Ex: Activated Charcoal adsorbs gases (C,
SO,, CO, Noble gases etc.)
Ni or Pt adsorbs H,gas (hydrogenation ofoils).
Animal charcoal adsorbs acetic acid molecules.
Coloured particles of molasses gets adsorbed
on activated charcoal hence molasses
decolourises.
I f a gas like O,, H2, CO, Cl2, NH3 or SO
taken in a closed vessel containing powdered
charcoal, then the pressure ofthe gas in the vessel
due to of gases
aecreases adsorption
charcoal.
AIS Solution ofan organic dye, say methylene blue
shaken with animal charcoal the filtrate turns
Colourless. Because the molecules ofthe dye are
adsorbed on the surface of charcoal.
f silica
Ar becomes dry in the presence of gel
silica gel|
ecause water molecules get adsorbed on the
surface ofthe gel
Adsorption is effective when the surface of
adsorbent is pure.
JEE-ADV CHEM-VOL-I
the
The process of removal of inmpurities from
surface ofadsorbent is called activation.
Ex: Charcoal is activated by heating at 300'C
1000°C in vacuum in presence of inert gas.
Absorption: Absoption is the bulk phenomenon
1.e., gas, liquid or solid molecules distributed
uniformly in solid or liquid.
Ex: i) Piece of chalk dipped in ink (chalk absorbs
ink) Sponge in water (sponge absorbs water)
Sorption: If both adsorption and absorption
takes place simultaneously then it is known as
sorption.
ex: Dying of fabrics, gases over metals
The term sorption was introduced by MC Bain.
Desorption: The process of removing an
adsorbed substance from a surface on which it
is adsorbed is called desorption.
Positive and Negative Adsorption:
When the concentration of adsorbate is more
on the surface ofthe adsorbent than in bulk, it is
called Postive adsorption. On the other hand,
ifthe concentration ofadsorbate is less ralative
to its concentration in bulk, it is called Negative
adsorption.
Eg: When concentrated solutioon of KCI is
shaken with wood charcol, it shows positive
adsorption but with a dilute solution ofKCI, it
shows negative adsorption
THERMODYNAMIC DATA
OFADSORPTION
Mechanism ofAdsorption: Adsorption arises
due to unbalanced forces acting on surfaces.
there a decrease in
is During adsorption, is always
residual surface energy which appears as heat.
There fore Adsorption is essentially an
exothermic process. (AH -ve)
=
on
During the process of adsorption, free
movement ofadsorbate becomes restricted i.e.
entropy ofsystem decreases. (AS = -ve).
Adsorption is, thus accompanied by decrease in
enthalpy (AH = -ve) and entropy (AS = -ve)
ofthe system.
>But for adsorption process in order to be
spontaneous the thermodynamic requirement is
negative AG (ie AH-TAS=-e).
 SURFACE CHEMISTRY
JEE-ADV CHEM-VO
AG Al1 TAS, AG can be negative it AH IS
Sufficient.y hig
ofThermodynamics
-

On the basis
negative to over conpensate
-

TAS (which is positive.)

less and less negative ultimately AH becomes.
As the adsorption procceds, AV/ becomcs
state cquilibrium is
reached.
At this
TAS and AG xconcs zero.
TYPES OFADSORPTIONS

ofa solid on account ofweak Van der orces

Waals' forces is termed
te
Accumlat ion ofgascs on the surface
physical adsorption or physisorption chemical bonds, the adsorption ist
held to the solid surface by
When gas molecules or atoms
or
are

chemisorption
term
as chemical adsorption

Physieal adsorption Chemical adsorption

Property forces Due to chemical forces
Nature of adsorption Due to v a n d e r w a l l 's
(Weak)
(Strong

Lo w
High
Enthalpy o f 80-240

adsorption
20-40
(AH) (KJ m o l )
Irreversible and occurs
Reversible and occurs rapidly
Reversibility o f
slowly
adsorption
L o w temperature (below the High temperatures
. Temp. at which (generally above the b.p.tof
b.p.t o f the adsorbate gas)
adsorption is more the adsorbate gas)
pronounced

Decreases with rise in

Increase with rise in
Effect of change in
temperature
temperature
Temperature

Specificity o f
Not specific generally takes Highly specific. Takes place
on specified surfaces
place on all surfaces
adsorption

Nature o f adsorbate Multilayered Only uni-layered

layers formedd

Increases with rise in pressure|

Pressure of the adsorbate
Effect o f pressure on
of adsorbate gas and finally has a negligible effect
adsorption attains a limiting value

Energy o f activation Insignificant i.e., very low Significant i.e., relatively

.
high
Depends on the adsorbate Depends on the adsorbate
10. Dependence on the
as well as a adsorbent. No
nature of the adsorbatd (gas) only. Easily liquefiable
gases are more readily correlation can be given.
& adsorbent
adsorbed

11. Ease of desorption Easy (vander waal's forces are| Not easy (chemical forces
involved) are involved)

12 Example Adsorption of H, gas on Adsorption "H," gas "N

powdered charcoal

The process of increasing the surface area 0

FACTORS EFFECTINGADSORPTION
adsorbent and making it a better adsorben
The extent ofAdsorption of Gases depends called activation ofthe Adsorbent.
on the following factors Porous charcoal, silica gel contain largesun
i) Surface of the Adsorbent: With|
area area.(charcoal is activated by heatmg in va
increase in the surface area ofthe solid rate of Determination of surface area of adsorbe
adsorption and extent of adsorption increases. IfV litre of gas is adsorbed at temperatu
Finely divided transition metals like Co,Ni, Pt| and Pressure P then the number ofgas mo
act as good adsorbents. adsorbed
PVN Ava vagadro's nu
RT
SURFACE CHEMISTRY JEE-ADV CHEM-VOL-I

Surface area ofadsorbent number of|

=

molecules. xArea of cross section of|

molecule( r )
soF 83K
195K
40
244K
ii) Nature of Gas (Adsorbate): Easily 30 273K
liquitiable gases adsorb more readily
20

SO,, NH,HCl and CO, adsorbed more than 0

H. P
Higher the critical teperature, greater is the ease 20 40 60
ofliquification of the gas and more is adsorption. Pressure in cm ofHg
Ig.ofactivated charcoal adsorbs about 400 mi
of SO, (Tc=430 K), 20 ml of CH, (Tc =356K)
Ease ofadsorptionof gases
log m
logp+logk
H.O> EtOH > SO,> SO,>Cl,>
slope = 1/n

NH,>HCI> CO, >

CH, > CO > 0, | log- Intercept= log k

>N, > H, > He

Competing or Preferential Adsorption:When log P
more than one type ofthe adsorbate species are Freundlich isotherm explains. the behaviour of
in contact with a particular adsorbent, there is a
competition between theirmolecules or paticles
adsorption in approximate manner. Here the
to be adsorbed on the solid surface. The one factor can have value between 0 and 1
n
which can form stronger bonds is adsorbed more
in preference to the other. This is known as (probable range 0.1 to 0.5)

competing adsorption. Adsorption If=00,then

chromatography is based upon this principle of | n m
constant,then adsorption
adsorptioon. is independent ofpressure.
iii) Pressure of the Gas: At constant
temperature. increase in pressure ofa gas leads If=1, then =K.P ie.a.p, adsorption
m
ncrease in the extent ofphysical adsorption. varies directly with pressure.
The effect ofpressure on chemisorption is zero. Both the conditions are supported by
At low pressure the physically adsorbed gas experimental results. The experimental isotherms
forms a monolayer. always seem to approach saturation at high
ADSORPTION ISOTHERMS pressure. This cannot be explained by Freundlich
FREUNDLICH, isotherm. Thus, it fails at high pressure.
Freundlich theory is applicable to physical
LANGMUIRADSORPTION
adsorption at modarate pressures only.
ISOTHERMS Langmuir Adsorption Isotherm: A solid
Freundlich isotherm: At constanttemperature surface is considered homogeneous, it contains
the amount ofthe gas adsorbed (x) on given mass a fixed number ofadsorption sites on the surface
to its
ofadsorbent (m) directly proportional
is ofit.
pressure. Each such site adsorbs a single molecule. This
means that adsorption is confined to a mono
- KP molecular layer.
m Adsorption is considered as an equilibrium
Kis constant of Freundlich adsorption isotherm process comprising ofvapourization(desorption)
and condensation(adsorption) occuring
simultaneously at a given temperature.
 JEE-ADV CHEM-VOL
SURFACE CHEMISTRY
is equal to
At equilibrium the rate ofevaporation
rate of condensation
Rate ofevaporation is proportional the
to area
adsorbed gas
When m is ploted aganst p Wegetstraigh
ofthe surface covered by the x

Rate oc area covered.

x6 line with slope and intercept
Rateofevaporation= K,
is proportional to the
Rate of condensation FREUNDLICHS ADSORPTION
of the gas and area
product of the pressure IN SOLUTION STATE
Rate cP x area
uncoveredon adsorbent. Adsorption in solutions:
uncovered.
During the adsorption if the concentration of

Rate ofcondensation= K.p(1-0) the solution decreases, it is called positiye

rates are equal
At equilibrium both adsorption.
The extent ofAdsorption (x/m) is related to the
K0=K_p(1-0) concentration of the solution through the
ofthe surface.
If o is covered fraction
mathematical formula=k.c"
bp where b= m
1+bp ka C= concentrationofthe solution.

Xkbp_. _p_
m 1+bp m 1+bp log= log k + ~loge
adsorbed m n
where x =
mass of a gas Extent ofadsorption decreases with an increase
m=mass ofadsorbent,
a =kb, b =ka/kd, p pressure. in temperature.
The above equation is called Langmuiradsorption The precipitate of Mg (OH), attains blue
Isothem
colour when precipitated in presence of
P
Magneson reagent (a violet dye) The colour
(x/ma is due to adsorption of Magneson.
solids have
P
be a straight Apart fromadsorption of the gases,
Thus a plot of (y/m against P wil! also the capacity to adsorb substances present
in solutions. For example, if we place a pieceo
line with slope and intercept charcoal in a litmus solution taken in a test tube
a a
and shake, the solution becomes colourless. Its
because ofadsorption of the litmus which ism
fact a dye, by the charcoal. Similarly, anim
charcoal decolorizes impure sugar solution
mechanisn
adsorbing colouring dye. The actual
not defnte
ofadsorption from the solution is
However, it is believed that it continuest
X/m
unimolecular layer is built up on the surface0
the adsorbent. The Freundlich dsorption
isothe
as well Langmuir adsorption isothemmd
as

applicable to the adsorption from the solutio

n the same way as from the gases. The effec
P
temperature is also similar. However, equillbr
concentration (C) is used in place ofequilibr
Above equation can be taken as
 SURFACE CHEMISTRY OA D
JEE-ADV CHEM-VOL-I
and the mathematical
ressure
P r e s

the two types of isotherms

are:
expressions for
X-k-C" (FreundlichAdsorption lIsotherm)
m

aC
or
m 14hangmuir Adsorption Isothem)
W.E-1: Per two
gram of charcoal, a
adsorbed by 0.1g and 0.2g gas is
at 10 torr
and
torr pressure respectively. Calculate 80
the n temperature (t°C)
value in Freundlich adsorption
isotherm. b. Chemisorption

Sol=K.P" (or)=| APPLICATIONS OFADSORPTION

Substituting the values, Production of high vacuum: The remaining
traces ofair can be adsorbed
0.1 (10 3/n by charcoal from
0.2 80 -
Therefore, the value ofn is 3
a vessel evacuated by a
very high vacuum.
vacuum

Gas masks: Gas mask (a device which

pump to give a

consists
ADSORPTION ISOBARS of activated charcoal or mixture ofadsorbents)
is usually used for
Temperature: Low temperatures favour
breathing in coal mines to
adsorb poisonous gases.
physical adsorption and hightemperatures favour
chemical adsorption or Control of humidity: Silica
chemisorption. (Si0, Jand
N , is physically adsorbed on ironat 463K but it
is chemisorbed at 723K alumina( AL,O,) gels are used as adsorbents
When temperature increases, rate of physical for removing moisture and
controlling humidity.
adsorption decreases. Removal of colouring matter from solutions:
In Chemical adsorption with increase Animal charcoal removes colours
temperature the magnitude of adsorption first
of| of solutions by
adsorbing coloured impurities.
increases and then decreases.
The graph plotted between x/m Heterogeneous catalysis: Adsorption of
vs reactants onthe solid surface of the
catalysts
temperature at constant pressure is called
increases the rate of reactants.There are
Freundlich adsorption isobars. many
gaseous reactions of industrial importance
involving solid catalysts. Manufacture of ammonia
using iron as a catalyst, manufacture of H,SO,
by contact process Pt/V,O, as catalyst and use
of finely divided nickel in the
hydrogenation of
oils are excellent examples of
heterogeneous
catalysis
Separation of inert gases: Due to the
difference in degree of adsorption of gases by
temperature (1°C) charcoal, a mixture of noble gases can be
separated in Dewar's method by adsorption on
a. Physical Adsorption coconut charcoal at different
temperatures.
 W.E-2: Onegram of charcwal adsorhs 10Oml of Adsorption indicators: Surfaccs ot
.511 CCOOto form a monolayerand precipitates such as silver halides
acid is| property of adsorbing some dyes li
thercbr the molariy of acidic fluoresccin, clc. and thercby pro.
reduccd to 0.40M. Calculate the surface
each characteristic colour at thecnd point,
area of thc charcoal adsorhed hy
molecule of acetic acid (surface arca of Chromatographic analysis: Chromulo
chanvalis 301 10 mg)
analysis based on the phenomenon of ad wlogyarp
finds a number ofapplications in analvi.
Sol. Nunmber of moles of acctic acid before the
industrial fields yUIca
100
adsoption - 05x- = 0.05 COLLOIDS,TRUE SOLUTION
1000
umher of moles of acetic acid atier the | SUSPENSIONS
ONS
100 Colloidal State:
adsorpiion =049 = 0.049
1000 The substances are clasSified nto crystaloid
Number of moles of acetic acid adsorbed colloids by Thomas Graham.
=

0.05-0.049 0.001 The substance which passes throuck

umber ofmolecules of aceticacid adsorbed=
0.001 6.023 10 =6.023 x10
Surtace area of the charcoal occupied by each|
acetic acid moiecuk
3.01x10
=5x10m m
6.023x10
Applications of adsorption:
In dyeing of cloth: Mordants such as alums
are used in dying ofcloth. They adsorb the dye
particles which. otherwise. do not stick to the
cloth
In ion-exchange resins: The organic polymer
containing groups lke-COOH, -SO,H, -NH,
etc.. possess the property ofselective adsorption
ofions from solutions. These are quite useful
in the softening ofwater and also in the
separation of the elements ofthe Lanthanide
series (also called rare earths).
3 Softening of hard water: The hard
made to pass through a column water
packed withis
zeolite. Ca, Mg jons which are responsible
for hardness get adsorbed on zeolite
4. Surfactants: Surfactantswill act as emulsifier
(which work on the princijple of adsorption) in
the manufacture ofemulsions
Osmotic pressure is the coligative property used
to determine the molecular weight ofa colloid
Froth floatation process: Alow grade sulphide|
ore is concentrated by separating it from silica
and other earthy matter by this method using pine
oil and froathing agent.
In curing diseases: A number of drugs are used
membrane is called crystalloid.
Eg: Sugar in water, Salt in water, Urea jn
acids and bases etc., mwae
The substance which disperses in a solve
can not pass through membrane is calledNenMa
ca
Eg: Glue:gum arabic, gelatn, agar-agaret
If the particle size of the solute in thehit
system is in range Im-1 a colloidalo
is formed.
Colloidal solutions are- Starch paste,gelai
glue added to hot water.
The system contains two phases one is "dis
phase", the other is "dispersion medium'
Solutions of chemical substances are bru
classified into true solutions and colloidalsolu
depending on the particle size.
I f the particle size of the solute in the b
system is less than Ime(10 m),atnues
is formed.
Examples for true solutions are solut
Common salt, sugar, acids,bases etc
Colloidal particles have an enormous
Can
area perunit mass as a result oftheirsize.
rfac
a cube with Icm side. It has a total sur
of 6cm. If it were divided equaly
cubes, the cubes would be the Sizeo
particles and will have a totalsurfa
area

60,000cm or 6m?. This largesurface

to kill germs bygetting adsorbed on them.
 industrial ficlds
COLLODS,TRUE SOLUTIONS

SUSPENSIONS

Colloidal State:

substances are
classified intocrystalloids n
and
The
Graham.
colloids by Thomas
which passes throughtho
The substance
membrane is called
crystalloid.

Salt in water, Urea in Water

ter,
Eg: Sugar in water,
acids and bases etc.,
solvent and
in a
The substance which disperses
can not pass through membrane is called colloid
etc
Eg: Glue: gum arabic, gelatn, agar-agar
in the binary
> If the particle size of the solute
colloidal solution
system is in range Imu-1u
a

is formed.
Colloidal solutions are - Starch paste, gelatin (or)

glue added to hot water.

The system contains two phases one is "dispersed
phase", the other is "dispersion medium".
Solutions of chemical substances are broady
classified into true solutions and colloidal solutions
depending on the particle size.
If the particle size of the solute in the binary
system isless than Impu(10m),atruesohition
is formed.
Examples for true solutions are solutionsof
Common salt, sugar, acids,bases etc.
Colloidal particles have an enormous sulace
area per unit mass as aresult oftheir size. Conside'
a cube with I cm side. It has a total surface an
of 6cm. If it were divided equally into 1
cubes, the cubes would be the size ofcollod
particles and will have a total surface area o
60,000cm or ómt. This large surftace area leau
linewith slope (1 andnterceptC)
FREUNDLICHS ADSORPTION
IN SOLUTION STATE
Adsorption in solutions:
During the adsorytm it the concentration o
the solution decrcascs, il is called positi.
tive
adsopt0n.
The extent ofAdsorption (x/m) is related to t.
the
concentration of the solution through th

mathenatical fommula-= k.c"

C= concentrationofthe solution.

log= log k + -logc

m
Extent ofadsorption decreases with an increase
m temperature.

The precipitate of Mg (OH ), attains blue

colour when precipitated in presence of
Magneson reagent (aviolet dye) The colour
is due to adsorption of Magneson.
Apart fromadsorption ofthe gases, solids have
also the capacity to adsorb substances present
in solutions. For example, ifwe place a piece of
charcoal in a litmus solution taken in a test tube
and shake, the solution becomes colourless. It is
because ofadsorption ofthe litmus which is in
fact a dye, by the charcoal. Similarly, animal
charcoal decolorizes impure sugar solution by
adsorbing colouring dye. The actual mechanism
definite.
ofadsorption from the solution is not a
continues till
However, it is believed that it
of
unimolecular layer is built up on the surface
the adsorbent. The Freundlich dsorptionisothem
are
as well as
Langmuir adsorption isotherm
applicable to the adsorption from the solutions
ol
n the same way as from the gases. The effect
temperature is also similar. However, equilibrium
oncentration (C) is used in placeofequilibrun